EP1476418B1 - Method for the production of amines - Google Patents

Method for the production of amines Download PDF

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Publication number
EP1476418B1
EP1476418B1 EP03706422A EP03706422A EP1476418B1 EP 1476418 B1 EP1476418 B1 EP 1476418B1 EP 03706422 A EP03706422 A EP 03706422A EP 03706422 A EP03706422 A EP 03706422A EP 1476418 B1 EP1476418 B1 EP 1476418B1
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Prior art keywords
reactor
nitroaromatics
hydrogen
reaction mixture
process according
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German (de)
French (fr)
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EP1476418A1 (en
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Peter Zehner
Jörn Müller
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups

Definitions

  • the invention relates to a process for the preparation of amines by hydrogenation of the corresponding nitroaromatics.
  • the hydrogenation is carried out in the art using hydrogenation catalysts in the liquid phase.
  • the compound to be reduced is usually mixed with the catalyst in a solvent and reduced batchwise in an autoclave or continuously in a stirred tank, a loop reactor, a bubble column or a reactor cascade.
  • disadvantages in the known processes of this type for example the necessity of discharging and especially the removal of deactivated catalyst components, which leads to catalyst losses.
  • the frequent side reactions which cause the formation of interfering substances, e.g. tarry constituents, and thus lead to yield reductions, a problem of many previously used methods.
  • WO 00/35852 describes a process for the preparation of amines by hydrogenation of the corresponding nitroaromatics, wherein the reaction in a vertical reactor, the length of which is greater than its diameter, with a arranged in the upper region of the reactor, downwardly directed jet nozzle through which the reactants and the reaction mixture are fed and with a trigger at any point of the reactor over which the reaction mixture is recycled in an external circulation by means of a conveying member of the jet nozzle, and a flow reversal in the lower region of the reactor is performed.
  • This reactor preferably has internal heat exchangers.
  • the educts are preferably fed via the jet nozzle in order to achieve the best possible mixing.
  • the aromatic amines can be prepared with a high space-time yield and with significant suppression of side reactions.
  • DE-C-198 44 901 describes a process for the preparation of aromatic amines by the liquid phase method in which the nitroaromatics are fed via a loop with holes in the reactor.
  • the loop can also be cooled by an external heat exchanger to eliminate the risk of overheating and thus thermal decomposition of the nitroaromatic.
  • a particularly good distribution of the nitro aromatic compounds in the reaction mixture should be achieved.
  • suitable reactors are loop reactors, bubble columns, preferably stirred tanks. Reactors with an internal loop flow, as in WO 00/35852 are not mentioned in this document. Especially in the case of such reactors, however, in the region below the flow reversal, the described enrichment of nitroaromatics of the liquid reaction mixture can occur.
  • the object of the invention was to develop a process for the preparation of aromatic amines in a flow reactor, in which a catalyst deactivation is avoided and by-product formation is reduced and no more nitroaromatics are present at the outlet of the reactor and can be operated with low catalyst concentrations.
  • the task could be surprisingly achieved in that in a reactor according to WO 00/35852 at least a portion of the hydrogen and / or nitroaromatics are metered into the liquid phase of the reactor so as to flow upward in the liquid reaction mixture.
  • the invention accordingly provides a process for preparing amines by hydrogenating the corresponding nitroaromatics, in a vertical reactor whose length is greater than its diameter, with a downwardly directed jet nozzle arranged in the upper region of the reactor, via which the reaction mixture and optionally a part of the reactants supplied be and with a trigger at any point of the reactor over which the reaction mixture is recycled in an external circulation by means of a conveying member of the jet nozzle, and a flow reversal in the lower region of the reactor, characterized in that at least a portion of the educts used hydrogen and / or nitroaromatics are metered into the liquid phase of the reactor so that they flow upwards in the liquid reaction mixture.
  • the hydrogen can be metered into both the upward flow of the liquid phase of the reactor above the flow reversal and in the downward flow of the liquid phase of the reactor below the flow reversal, since it due to its low density in each case in the flowing liquid phase upwards.
  • the dosage of the nitroaromatics is such that they are metered into the upward flow within the liquid phase of the reactor, ie above the flow reversal.
  • the reactor has in its lower part a baffle plate arranged perpendicular to the reactor wall.
  • the nitroaromatics and optionally a portion or all of the hydrogen above the baffle plate are metered into the upward flow within the reactor.
  • a concentric plug-in tube is additionally provided parallel to the reactor wall in the reactor, through which the reaction mixture from the jet nozzle to the flow reversal, in particular the baffle plate, is directed.
  • the entire amount of hydrogen and nitroaromatics can be fed to the reactor as described.
  • part of the added hydrogen is metered into the outer circulation of the reactor.
  • the hydrogen is in dosed the suction side of the outer circuit.
  • the amount of hydrogen metered into the external circuit should be such that the reaction mixture in the external circuit has a gas content in the range between 3 and 15% by weight, preferably between 5 and 10% by weight. In this quantitative range, sufficient supply of the reaction mixture with hydrogen is possible by optimal dispersion of the gas in the liquid reaction mixture. At higher gas contents in the loop, there may also be problems with the circulation pump, lower gas levels in the loop have no more positive effect on the implementation.
  • the dosage of hydrogen at the point according to the invention can be carried out in the simplest case via one or more inlet tubes. Better distribution of the hydrogen can be achieved, for example, by using a multi-ported priming device. Due to the design of the reactor used for the process according to the invention preferably a distributor ring is used. Other preferred devices for supplying the hydrogen are distribution cores or sintered plates.
  • the feeding of the nitroaromatics in addition to the feed at the point according to the invention, also take place in the outer cycle or preferably in the nozzle.
  • the dosage in the external circulation is less preferred, because there the mixing is worse. Dosing into the nozzle can take place in the immediate vicinity of the nozzle outlet. An even better mixing can be achieved if the metering takes place at the end of the nozzle, which is located on the outer pumping line, or in the outer pumping line directly at the nozzle.
  • the dosage of the nitroaromatics at the point according to the invention can also be effected via introduction tubes, distribution stars, ring lines or other devices which allow a good distribution of the nitroaromatics.
  • the metering device for the nitroaromatics is, as stated, mounted in the lower part of the reactor above the flow reversal, taking care that the nitroaromatics are metered in the upward flow.
  • the metering device for the nitroaromatics between the baffle plate and the concentric spigot is attached.
  • the feeding of the hydrogen is also carried out in the lower part of the reactor so that it rises in the liquid reaction mixture to the top.
  • the feed is made between reactor bottom and plug-in tube.
  • ring lines for metering hydrogen and / or nitroaromatics When using ring lines for metering hydrogen and / or nitroaromatics at the point according to the invention, these have a sufficient number of holes for optimum distribution. This is preferably in the range between 2 and 500, in particular between 2 and 200. As the bores pass through the educts, a pressure loss occurs. In the case of the nitroaromatics, this is preferably between 0.1 and 10 bar, in particular between 0.3 and 3 bar, with hydrogen preferably between 0.05 and 0.15 bar.
  • the mass flow in the metering device should be monitored.
  • the mass flow value drops, the nitroaromatics must be removed from the dosing device. This can be done for example by rinsing with warm water.
  • Another possibility of reducing the risk of thermal decomposition of the nitroaromatics consists in the cooling of the metering device. This variant is not preferred for the method according to the invention, since the cross-section of the metering device is increased by the cooling jacket, which can lead to an impairment of the flow in the reactor.
  • the reactor corresponds to the in WO 00/35852 described reactor.
  • the jet nozzle of the reactor can be designed as a one-, two- or three-fluid nozzle. If all of the hydrogen and the total amount of nitroaromatics are metered in at the bottom, a one-fluid nozzle is preferred. In the single-component nozzle, only the liquid reaction mixture is injected and the hydrogen and the nitroaromatics are fed to the reactor at the preferred locations.
  • An advantage of this embodiment is the simple design of this nozzle, disadvantageous is the poorer dispersion of the hydrogen in the reaction mixture.
  • the hydrogen and the nitroaromatics can be supplied and dispersed at the nozzle center or via annular gaps. In this embodiment of the method, the dispersion of the hydrogen in the reaction mixture is much better.
  • the reactor is preferably, regardless of the type of nitro compounds used, a pressure of 5 to 100 bar, preferably 10 to 50 bar, and an operating temperature of 80 to 200 ° C, preferably 100 to 150 ° C, maintained.
  • the power input is preferably at the nozzle 15 to 30 kW / 1, in the entire reaction system 3 to 10 W / 1.
  • Product discharge from the system takes place continuously at any point.
  • the product discharge preferably takes place in the lower reactor region at the bottom of the reactor or in particular from the outer loop flow via a catalyst separation unit or without such.
  • This separation unit can be a gravity separator, z.
  • a settler As a settler, a cross-flow filter or a centrifuge.
  • the catalyst can be separated from the product and then returned to the reactor system.
  • the product is discharged while retaining the catalyst.
  • the amine can then be purified by the usual and known methods, for example by distillation or extraction.
  • the mono- and / or Polynitrotagen in pure form, as a mixture with the corresponding mono- and / or polyamine, as a mixture with the corresponding mono- and / or polyamine and water or as a mixture with the corresponding mono- and / or polyamine, water and a particular alcoholic solvent used.
  • the aromatic mono- and / or Polynitrotagen is finely divided into the mixture.
  • aromatic nitro compounds having one or more nitro groups and 6 to 18 carbon atoms, bsp.
  • Nitrobenzenes such as o-, m-, p-nitrobenzene, 1,3-dinitrobenzene, nitrotoluenes, such as 2,4-, 2,6-dinitrotoluene, 2,4,6-trinitrotoluene, nitroxylols, such as 1,2 Dimethyl 3-, 1,2-dimethyl-4-, 1,4-dimethyl-2-, 1,3-dimethyl-2-, 2,4-dimethyl-1- and 1,3-dimethyl-5-nitrobenzene , Nitronaphthalenes such as 1-, 2-nitronaphthalene, 1,5 and 1,8-dinitronaphthalene, chloronitrobenzenes such as 2-chloro-1,3-, 1-chloro-2,4-dinitrobenzene, o-, m- , p-chloro
  • novel aromatic nitro compounds preferably mononitrobenzene, methylnitrobenzene or methylnitrotoluene, and in particular 2,4-dinitrotoluene or its technical mixtures with 2,6-dinitrotoluene, these mixtures preferably up to 35 weight percent, based on the total mixture of 2 , 6-dinitrotoluene having proportions of 1 to 4 percent of vicinal DNT and 0.5 to 1.5% of 2,5- and 3,5-dinitrotoluene, hydrogenated to the corresponding amines.
  • the inventive method can be used advantageously.
  • the formation of high molecular weight, tarry by-products, which led in the methods of the prior art to yield losses and for bonding and thus premature deactivation of the catalyst could be almost completely suppressed.
  • the cleaning of the TDA is less complicated than in the methods of the prior art.
  • the hydrogenation of the dinitrotoluene can be carried out in solution.
  • the solvents used are the customary substances, in particular lower alcohols, preferably ethanol.
  • the hydrogenation is carried out without a solvent. This has the advantages that the volume of the reaction mixture is lower, which allows smaller dimensions of the reactor and the pumps and pipelines, that side reactions between the solvent and the starting materials are excluded and the cost of working up the end products is reduced.
  • the known hydrogenation catalysts for aromatic nitro compounds are used. It is possible to use homogeneous and / or in particular heterogeneous catalysts.
  • the heterogeneous catalysts are used in finely divided state and are finely suspended in the reaction suspension before.
  • Suitable catalysts are metals of VIII.
  • Subgroup of the Periodic Table which may be applied to support materials such as activated carbon or oxides of aluminum, silicon or other materials. Raney nickel and / or supported catalysts based on nickel, palladium and / or platinum are preferably used.
  • the dispersion of the individual reactants, in conjunction with the other reaction parameters, achieves intensive mixing of all components, with high mass transfer coefficients and high volume-specific phase boundary surfaces.
  • the arrangement of the cooling tubes in the reactor parallel to the reactor walls has an almost complete gradient freedom of the reactor contents with respect to the reaction temperature result. By avoiding local overheating side reactions are clearly suppressed and catalyst deactivation largely avoided. It is thus achieved even at low catalyst concentrations high space-time yields at high selectivity.
  • the process according to the invention is particularly suitable for the hydrogenation of dinitrotoluene to toluenediamine. Precisely in the case of this reaction, pronounced side reactions with the formation of tarry constituents occur in the prior art processes.
  • the preparation of toluenediamine by the novel process is carried out at the customary for the production of aromatic amines, the above temperatures and pressures.
  • the method according to the invention has several advantages.
  • the distribution of the starting materials in the reaction mixture is improved, which leads to low levels of by-products and low deactivation of the catalyst.
  • the implementation of the nitroaromatics is more complete, that is, the concentration of nitroaromatics at the outlet of the reactor drops significantly. This offers the possibility of increasing the space-time yield in the reactor.
  • the aging of the catalyst is also reduced.
  • the residence time of the nitroaromatics in the reactor is increased, thereby, in principle, the catalyst concentration can be reduced.
  • the energy input into the reactor can be reduced because the hydrogen increases the gas content and thus the mass transport performance in the annulus of the reactor and stabilizes the internal loop flow by its buoyancy.
  • the power input through the jet nozzle and thus also the amount of the outer circuit can be significantly reduced. In addition to the energy savings, this also leads to a lower mechanical stress and thus to a longer life of the catalyst.
  • the reaction volume of the reactor is about 12 m 3 .
  • the reactor is provided with 350 parallel field tubes (4), which correspond to a total cooling area of about 300 m 2 .
  • the amount of cooling water fed into the field tubes was 250 m 3 / h, the temperature of the cooling water fed into the field tubes was 50 ° C.
  • the reaction proceeded under almost isothermal conditions, since the resulting heat of reaction was already removed at the site of its formation.
  • the maximum reaction temperature in the lower third of the reactor was 125 ° C. 4.64 t / h of a corresponding diaminotoluene mixture and 2.74 t / h of water were continuously withdrawn from the reactor via a cross-flow filter installed in the outer circuit, which gave a space-time yield of 400 kg of amine mixture / (m 3 ⁇ H) corresponded.
  • the yield of diamine was, based on dinitrotoluene used,> 99%.

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Abstract

Amines are prepared by hydrogenation of the corresponding nitroaromatics in a vertical reactor whose length is greater than its diameter and which has in its upper region a downward-directed jet nozzle via which the reaction mixture and, if desired, part of the starting materials are introduced, has an outlet at any point on the reactor via which the reaction mixture is conveyed in an external circuit by means of a transport device back to the jet nozzle and has a flow reversal in its lower region, wherein at least part of the hydrogen and/or nitroaromatic starting materials used is fed into the liquid phase of the reactor in such a way that they travel upward in the liquid phase.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Aminen durch Hydrierung der entsprechenden Nitroaromaten.The invention relates to a process for the preparation of amines by hydrogenation of the corresponding nitroaromatics.

Die Herstellung von Aminen, insbesondere aromatischen Aminen, durch Hydrierung der entsprechenden Nitroaromaten ist seit langem bekannt und vielfach in der Literatur beschrieben.The preparation of amines, especially aromatic amines, by hydrogenation of the corresponding nitroaromatics has long been known and widely described in the literature.

Zumeist wird die Hydrierung in der Technik unter Einsatz von Hydrierkatalysatoren in der Flüssigphase durchgeführt. Dabei wird die zu reduzierende Verbindung zumeist in einem Lösungsmittel mit dem Katalysator vermischt und diskontinuierlich in einem Autoklaven oder kontinuierlich in einem Rührkessel, einem Schlaufenreaktor, einer Blasensäule oder einer Reaktorkaskade reduziert. Bei den bekannten derartigen Verfahren gibt es eine Reihe von Nachteilen, beispielsweise die Notwendigkeit des Austragens und besonders des Ausschleusens desaktivierter Katalysatoranteile, was zu Katalysatorverlusten führt. Ferner stellen die häufig auftretenden Nebenreaktionen, die zur Bildung störender Substanzen, wie z.B. teerartiger Bestandteile, und damit zu Ausbeuteminderungen führen, ein Problem vieler bislang verwendeter Verfahren dar.In most cases, the hydrogenation is carried out in the art using hydrogenation catalysts in the liquid phase. In this case, the compound to be reduced is usually mixed with the catalyst in a solvent and reduced batchwise in an autoclave or continuously in a stirred tank, a loop reactor, a bubble column or a reactor cascade. There are a number of disadvantages in the known processes of this type, for example the necessity of discharging and especially the removal of deactivated catalyst components, which leads to catalyst losses. Furthermore, the frequent side reactions which cause the formation of interfering substances, e.g. tarry constituents, and thus lead to yield reductions, a problem of many previously used methods.

In WO 00/35852 wird ein Verfahren zur Herstellung von Aminen durch Hydrierung der entsprechenden Nitroaromaten beschrieben, bei dem die Reaktion in einem vertikalen Reaktor, dessen Länge größer ist als sein Durchmesser, mit einer im oberen Bereich des Reaktors angeordneten, nach unten gerichteten Strahldüse, über die die Edukte sowie das Reaktionsgemisch zugeführt werden sowie mit einem Abzug an einer beliebigen Stelle des Reaktors, über den das Reaktionsgemisch in einem äußeren Kreislauf mittels eines Förderorgans der Strahldüse wieder zugeführt wird, sowie einer Strömungsumkehr im unteren Bereich des Reaktors durchgeführt wird, verwendet. Dieser Reaktor weist vorzugsweise innenliegende Wärmetauscher auf. Die Edukte werden vorzugsweise über die Strahldüse zugeführt, um eine möglichst gute Durchmischung zu erreichen. Bei dem in WO 00/35852 beschriebenen Verfahren können die aromatischen Amine mit einer hohen Raum-Zeit-Ausbeute und bei deutlicher Unterdrückung von Nebenreaktionen hergestellt werden.In WO 00/35852 describes a process for the preparation of amines by hydrogenation of the corresponding nitroaromatics, wherein the reaction in a vertical reactor, the length of which is greater than its diameter, with a arranged in the upper region of the reactor, downwardly directed jet nozzle through which the reactants and the reaction mixture are fed and with a trigger at any point of the reactor over which the reaction mixture is recycled in an external circulation by means of a conveying member of the jet nozzle, and a flow reversal in the lower region of the reactor is performed. This reactor preferably has internal heat exchangers. The educts are preferably fed via the jet nozzle in order to achieve the best possible mixing. At the in WO 00/35852 described processes, the aromatic amines can be prepared with a high space-time yield and with significant suppression of side reactions.

Es hat sich allerdings gezeigt, dass im Reaktor, insbesondere in der nach unten gerichteten Strömung unterhalb der Strömungsumkehr der Flüssigphase, insbesondere in der Nähe des Reaktorausgangs, mitunter erhöhte Gehalte an Nitroaromaten auftreten, insbesondere bei Verwendung geringer Katalysatorgehalte.However, it has been shown that in the reactor, in particular in the downward flow below the flow reversal of the liquid phase, in particular in the vicinity of the reactor outlet, sometimes increased levels of nitroaromatics occur, especially when using low catalyst contents.

In DE-C-198 44 901 wird ein Verfahren zur Herstellung von aromatischen Aminen nach dem Sumpfphasenverfahren beschrieben, bei dem die Nitroaromaten über eine Ringleitung mit Löchern in den Reaktor eingespeist werden. Die Ringleitung kann auch über einen außenliegenden Wärmeübertrager gekühlt werden, um die Gefahr einer Überhitzung und damit einer thermischen Zersetzung der Nitroaromaten auszuschließen. Bei diesem Verfahren soll eine besonders gute Verteilung der Nitroaromaten in der Reaktionsmischung erreicht werden. Als geeignete Reaktoren werden beispielsweise Loop-Reaktoren, Blasensäulen, vorzugsweise Rührkessel beschrieben. Reaktoren mit einer inneren Schlaufenströmung, wie in WO 00/35852 beschrieben, werden in diesem Dokument nicht erwähnt. Speziell bei derartigen Reaktoren kann es jedoch im Bereich unterhalb der Strömungsumkehr zu der beschriebenen Anreicherung von Nitroaromaten der flüssigen Reaktionsmischung kommen. Dies kann daran liegen, daß die Verweilzeit in der nach unten gerichteten, schnellfließenden Strömung und im Bereich der Strömungsumkehr an der Prallplatte zu gering für eine vollständige Umsetzung der Nitroaromaten ist. Da es sich bei der nach unten gerichteten Strömung um ein schnell fließendes Gemisch handelt, ist die Verweilzeit in diesem Teil des Reaktors ohnehin sehr gering. Dieser Effekt tritt insbesondere bei der Verwendung geringer Gehalte an Katalysator beziehungsweise bei Katalysatoren mit einer geringen Aktivität auf.In DE-C-198 44 901 describes a process for the preparation of aromatic amines by the liquid phase method in which the nitroaromatics are fed via a loop with holes in the reactor. The loop can also be cooled by an external heat exchanger to eliminate the risk of overheating and thus thermal decomposition of the nitroaromatic. In this method, a particularly good distribution of the nitro aromatic compounds in the reaction mixture should be achieved. Examples of suitable reactors are loop reactors, bubble columns, preferably stirred tanks. Reactors with an internal loop flow, as in WO 00/35852 are not mentioned in this document. Especially in the case of such reactors, however, in the region below the flow reversal, the described enrichment of nitroaromatics of the liquid reaction mixture can occur. This may be because the residence time in the downflowing, fast flowing flow and in the area of flow reversal at the baffle plate is too low for complete reaction of the nitroaromatics. Since the downward flow is a fast-flowing mixture, the residence time in this part of the reactor is very low anyway. This effect occurs in particular when using small amounts of catalyst or catalysts having a low activity.

Aufgabe der Erfindung war es, ein Verfahren zur Herstellung aromatischen Aminen in einem Strömungsreaktor zu entwickeln, bei dem eine Katalysatordesaktivierung vermieden und die Nebenproduktbildung reduziert wird sowie am Ausgang des Reaktors keine Nitroaromaten mehr vorliegen und das mit niedrigen Katalysatorkonzentrationen betrieben werden kann.The object of the invention was to develop a process for the preparation of aromatic amines in a flow reactor, in which a catalyst deactivation is avoided and by-product formation is reduced and no more nitroaromatics are present at the outlet of the reactor and can be operated with low catalyst concentrations.

Die Aufgabe konnte überraschenderweise dadurch gelöst werden, daß bei einem Reaktor gemäß WO 00/35852 zumindest ein Teil des Wasserstoffs und/oder der Nitroaromaten in die Flüssigphase des Reaktors so eindosiert werden, daß sie in der flüssigen Reaktionsmischung nach oben strömen.The task could be surprisingly achieved in that in a reactor according to WO 00/35852 at least a portion of the hydrogen and / or nitroaromatics are metered into the liquid phase of the reactor so as to flow upward in the liquid reaction mixture.

Gegenstand der Erfindung ist demzufolge ein Verfahren zur Herstellung von Aminen durch Hydrierung der entsprechenden Nitroaromaten, in einem vertikalen Reaktor, dessen Länge größer ist als sein Durchmesser, mit einer im oberen Bereich des Reaktors angeordneten, nach unten gerichteten Strahldüse, über die das Reaktionsgemisch sowie gegebenenfalls ein Teil der Edukte zugeführt werden sowie mit einem Abzug an einer beliebigen Stelle des Reaktors, über den das Reaktionsgemisch in einem äußeren Kreislauf mittels eines Förderorgans der Strahldüse wieder zugeführt wird, sowie einer Strömungsumkehr im unteren Bereich des Reaktors, dadurch gekennzeichnet, daß zumindest ein Teil der eingesetzten Edukte Wasserstoff und/oder Nitroaromaten in die Flüssigphase des Reaktors so eindosiert werden, daß sie in der flüssigen Reaktionsmischung nach oben strömen.The invention accordingly provides a process for preparing amines by hydrogenating the corresponding nitroaromatics, in a vertical reactor whose length is greater than its diameter, with a downwardly directed jet nozzle arranged in the upper region of the reactor, via which the reaction mixture and optionally a part of the reactants supplied be and with a trigger at any point of the reactor over which the reaction mixture is recycled in an external circulation by means of a conveying member of the jet nozzle, and a flow reversal in the lower region of the reactor, characterized in that at least a portion of the educts used hydrogen and / or nitroaromatics are metered into the liquid phase of the reactor so that they flow upwards in the liquid reaction mixture.

Der Wasserstoff kann dabei sowohl in die nach oben gerichtete Strömung der flüssigen Phase des Reaktors oberhalb der Strömungsumkehr als auch in die nach unten gerichtete Strömung der flüssigen Phase des Reaktors unterhalb der Strömungsumkehr eindosiert werden, da er auf Grund seiner geringen Dichte in jedem Falle in der flüssigen Phase nach oben strömt.The hydrogen can be metered into both the upward flow of the liquid phase of the reactor above the flow reversal and in the downward flow of the liquid phase of the reactor below the flow reversal, since it due to its low density in each case in the flowing liquid phase upwards.

Die Dosierung der Nitroaromaten erfolgt so, dass sie in die nach oben gerichtete Strömung innerhalb der Flüssigphase des Reaktors, also oberhalb der Strömungsumkehr, eindosiert werden.The dosage of the nitroaromatics is such that they are metered into the upward flow within the liquid phase of the reactor, ie above the flow reversal.

In einer bevorzugten Ausführungsform der Erfindung weist der Reaktor in seinem unteren Teil eine senkrecht zur Reaktorwand angeordnete Prallplatte auf. Bei dieser Ausführungsform werden die Nitroaromaten sowie gegebenenfalls ein Teil oder der gesamte Wasserstoff oberhalb der Prallplatte in die nach oben gerichtete Strömung innerhalb des Reaktors eindosiert. In einer weiteren bevorzugten Ausführungsform der Erfindung ist im Reaktor zusätzlich ein konzentrisches Einsteckrohr parallel zur Reaktorwand angebracht, durch das die Reaktionsmischung aus der Strahldüse zu der Strömungsumkehr, insbesondere der Prallplatte, gelenkt wird.In a preferred embodiment of the invention, the reactor has in its lower part a baffle plate arranged perpendicular to the reactor wall. In this embodiment, the nitroaromatics and optionally a portion or all of the hydrogen above the baffle plate are metered into the upward flow within the reactor. In a further preferred embodiment of the invention, a concentric plug-in tube is additionally provided parallel to the reactor wall in the reactor, through which the reaction mixture from the jet nozzle to the flow reversal, in particular the baffle plate, is directed.

Wie ausgeführt, kann die gesamte Menge des Wasserstoffs und der Nitroaromaten wie beschrieben dem Reaktor zugeführt werden.As stated, the entire amount of hydrogen and nitroaromatics can be fed to the reactor as described.

Es ist ebenfalls möglich, entweder nur den Wasserstoff oder nur die Nitroaromaten an der erfindungsgemäßen Stelle in den Reaktor einzudosieren und das andere Edukt ausschließlich an einer anderen Stelle, vorzugsweise über die Strahldüse oder durch Dosierung in den äußeren Kreislauf, dem Reaktor zuzuführen. Der Wasserstoff, der nicht an der erfindungsgemäßen Stelle dem Reaktor zugeführt wird, kann auch an einer beliebigen Stelle in den Gasraum des Reaktors dosiert werden. Von dort wird er durch den Treibstrahl in die Flüssigphase des Reaktors eingeschlagen.It is likewise possible to meter either only the hydrogen or only the nitroaromatics at the point according to the invention into the reactor and to feed the other starting material exclusively at another point, preferably via the jet nozzle or by metering into the external circuit, to the reactor. The hydrogen which is not supplied to the reactor at the point according to the invention can also be metered at any point into the gas space of the reactor. From there it is smashed by the propulsion jet into the liquid phase of the reactor.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird ein Teil des zugesetzten Wasserstoffs in den äußeren Umlauf des Reaktors dosiert. Vorzugsweise wird der Wasserstoff in die Saugseite des äußeren Kreislaufs dosiert. Die Menge des in den äußeren Kreislauf dosierten Wasserstoffs sollte so bemessen sein, daß die Reaktionsmischung im äußeren Kreislauf einen Gasgehalt im Bereich zwischen 3 und 15 Gew.-%, vorzugsweise zwischen 5 und 10 Gew.-%, aufweist. In diesem Mengenbereich ist durch eine optimale Dispergierung des Gases in der flüssigen Reaktionsmischung eine ausreichende Versorgung der Reaktionsmischung mit Wasserstoff möglich. Bei höheren Gasgehalten in der Ringleitung kann es außerdem zu Problemen mit der Kreislaufpumpe kommen, geringere Gasgehalte in der Ringleitung haben keinen positiven Effekt mehr auf die Umsetzung.In a preferred embodiment of the process according to the invention, part of the added hydrogen is metered into the outer circulation of the reactor. Preferably, the hydrogen is in dosed the suction side of the outer circuit. The amount of hydrogen metered into the external circuit should be such that the reaction mixture in the external circuit has a gas content in the range between 3 and 15% by weight, preferably between 5 and 10% by weight. In this quantitative range, sufficient supply of the reaction mixture with hydrogen is possible by optimal dispersion of the gas in the liquid reaction mixture. At higher gas contents in the loop, there may also be problems with the circulation pump, lower gas levels in the loop have no more positive effect on the implementation.

Die Dosierung des Wasserstoffs an der erfindungsgemäßen Stelle kann im einfachsten Falle über ein oder mehrere Einleitungsrohre erfolgen. Eine bessere Verteilung des Wasserstoffs kann beispielsweise durch Verwendung einer Einleitungsvorriuhtung mit mehreren Öffnungen erreicht werden. Auf Grund der Bauart des für das erfindungsgemäße Verfahren eingesetzten Reaktors kommt vorzugsweise ein Verteilerring zum Einsatz. Andere bevorzugte Vorrichtungen zur Einspeisung des Wasserstoffs sind Verteilersterne oder Sinterplatten.The dosage of hydrogen at the point according to the invention can be carried out in the simplest case via one or more inlet tubes. Better distribution of the hydrogen can be achieved, for example, by using a multi-ported priming device. Due to the design of the reactor used for the process according to the invention preferably a distributor ring is used. Other preferred devices for supplying the hydrogen are distribution cores or sintered plates.

Die Einspeisung der Nitroaromaten kann, neben der Einspeisung an der erfindungsgemäßen Stelle, auch in den äußeren Kreislauf oder vorzugsweise in die Düse erfolgen. Die Dosierung in den äußeren Kreislauf ist weniger bevorzugt, da dort die Vermischung schlechter ist. Die Dosierung in die Düse kann in unmittelbarer Nähe des Düsenausgangs erfolgen. Eine noch bessere Durchmischung kann erreicht werden, wenn die Dosierung an dem Ende der Düse, das an der äußeren Umpumpleitung befindlich ist, oder in die äußere Umpumpleitung unmittelbar an der Düse erfolgt.The feeding of the nitroaromatics, in addition to the feed at the point according to the invention, also take place in the outer cycle or preferably in the nozzle. The dosage in the external circulation is less preferred, because there the mixing is worse. Dosing into the nozzle can take place in the immediate vicinity of the nozzle outlet. An even better mixing can be achieved if the metering takes place at the end of the nozzle, which is located on the outer pumping line, or in the outer pumping line directly at the nozzle.

Die Dosierung der Nitroaromaten an der erfindungsgemäßen Stelle kann ebenfalls über Einleitungsrohre, Verteilersterne, Ringleitungen oder andere Vorrichtungen, die eine gute Verteilung der Nitroaromaten ermöglichen, erfolgen.The dosage of the nitroaromatics at the point according to the invention can also be effected via introduction tubes, distribution stars, ring lines or other devices which allow a good distribution of the nitroaromatics.

Die Dosiereinrichtung für die Nitroaromaten wird, wie ausgeführt, im unteren Teil des Reaktors oberhalb der Strömungsumkehr angebracht, wobei darauf zu achten ist, daß die Nitroaromaten in die nach oben gerichtete Strömung dosiert werden. Bevorzugt wird die Dosiereinrichtung für die Nitroaromaten zwischen der Prallplatte und dem konzentrischen Einsteckrohr angebracht.The metering device for the nitroaromatics is, as stated, mounted in the lower part of the reactor above the flow reversal, taking care that the nitroaromatics are metered in the upward flow. Preferably, the metering device for the nitroaromatics between the baffle plate and the concentric spigot is attached.

Die Einspeisung des Wasserstoffs wird ebenfalls im unteren Teil des Reaktors so vorgenommen, daß er in der flüssigen Reaktionsmischung nach oben steigt. Besonders bevorzugt wird die Einspeisung zwischen Reaktorboden und Einsteckrohr vorgenommen.The feeding of the hydrogen is also carried out in the lower part of the reactor so that it rises in the liquid reaction mixture to the top. Particularly preferably, the feed is made between reactor bottom and plug-in tube.

Bei der Verwendung von Ringleitungen zur Dosierung von Wasserstoff und/oder Nitroaromaten an der erfindungsgemäßen Stelle weisen diese eine zur optimalen Verteilung ausreichende Anzahl von Bohrungen auf. Diese liegt vorzugsweise im Bereich zwischen 2 und 500, insbesondere zwischen 2 und 200. Beim Durchströmen der Bohrungen durch die Edukte tritt ein Druckverlust auf. Dieser liegt bei den Nitroaromaten vorzugsweise zwischen 0,1 und 10 bar, insbesondere zwischen 0,3 und 3 bar, beim Wasserstoff vorzugsweise zwischen 0,05 und 0,15 bar.When using ring lines for metering hydrogen and / or nitroaromatics at the point according to the invention, these have a sufficient number of holes for optimum distribution. This is preferably in the range between 2 and 500, in particular between 2 and 200. As the bores pass through the educts, a pressure loss occurs. In the case of the nitroaromatics, this is preferably between 0.1 and 10 bar, in particular between 0.3 and 3 bar, with hydrogen preferably between 0.05 and 0.15 bar.

Um im Falle der Nitroaromaten, die sich bei den im Reaktor herrschenden Temperaturen thermisch zersetzen können, gefährliche Betriebszustände zu vermeiden, sollte der Massestrom in der Dosiereinrichtung überwacht werden. Wenn der Wert für den Massestrom abfällt, müssen die Nitroaromaten aus der Dosiervorrichtung entfernt werden. Dies kann beispielsweise durch Spülen mit warmen Wasser erfolgen. Eine weitere Möglichkeit der Reduzierung der Gefahr einer thermischen Zersetzung der Nitroaromaten besteht in der Kühlung der Dosiervorrichtung. Diese Variante ist für das erfindungsgemäße Verfahren nicht bevorzugt, da durch den Kühlmantel der Querschnitt der Dosiervorrichtung erhöht wird, was zu einer Beeinträchtigung der Strömung im Reaktor führen kann.In order to avoid dangerous operating conditions in the case of nitroaromatics, which can thermally decompose at the temperatures prevailing in the reactor, the mass flow in the metering device should be monitored. When the mass flow value drops, the nitroaromatics must be removed from the dosing device. This can be done for example by rinsing with warm water. Another possibility of reducing the risk of thermal decomposition of the nitroaromatics consists in the cooling of the metering device. This variant is not preferred for the method according to the invention, since the cross-section of the metering device is increased by the cooling jacket, which can lead to an impairment of the flow in the reactor.

Abgesehen von der Dosierung der Edukte entspricht der Reaktor dem in WO 00/35852 beschriebenen Reaktor.Apart from the dosage of the starting materials, the reactor corresponds to the in WO 00/35852 described reactor.

Die Strahldüse des Reaktors kann als Ein-, Zwei- oder Dreistoffdüse ausgelegt werden. Wenn der gesamte Wasserstoff und die gesamte Menge an Nitroaromaten am Boden zudosiert wird, ist eine Einstoffdüse bevorzugt. Bei der Einstoffdüse wird nur das flüssige Reaktionsgemisch eingedüst und der Wasserstoff und die Nitroaromaten an den bevorzugten Stellen dem Reaktor zugeführt. Vorteilhaft bei dieser Ausgestaltung ist der einfache Aufbau dieser Düse, nachteilig ist die schlechtere Dispergierung des Wasserstoffs im Reaktionsgemisch. Bei der Zwei- bzw. Dreistoffdüse, die im Aufbau aufwendiger ist, können der Wasserstoff sowie die Nitroaromaten düsenmittig oder über Ringspalte zugeführt und dispergiert werden. Bei dieser Ausgestaltung des Verfahrens ist die Dispergierung des Wasserstoffs in der Reaktionsmischung wesentlich besser.The jet nozzle of the reactor can be designed as a one-, two- or three-fluid nozzle. If all of the hydrogen and the total amount of nitroaromatics are metered in at the bottom, a one-fluid nozzle is preferred. In the single-component nozzle, only the liquid reaction mixture is injected and the hydrogen and the nitroaromatics are fed to the reactor at the preferred locations. An advantage of this embodiment is the simple design of this nozzle, disadvantageous is the poorer dispersion of the hydrogen in the reaction mixture. In the two-fluid or three-fluid nozzle, which is more complex in construction, the hydrogen and the nitroaromatics can be supplied and dispersed at the nozzle center or via annular gaps. In this embodiment of the method, the dispersion of the hydrogen in the reaction mixture is much better.

Im Reaktor wird vorzugsweise, unabhängig von der Art der eingesetzten Nitroverbindungen, ein Druck von 5 bis 100 bar, bevorzugt 10 bis 50 bar, und eine Betriebstemperatur von 80 bis 200°C, bevorzugt 100 bis 150°C, aufrechterhalten. Der Leistungseintrag beträgt vorzugsweise an der Düse 15 bis 30 kW/1, im gesamten Reaktionssystem 3 bis 10 W/1.In the reactor is preferably, regardless of the type of nitro compounds used, a pressure of 5 to 100 bar, preferably 10 to 50 bar, and an operating temperature of 80 to 200 ° C, preferably 100 to 150 ° C, maintained. The power input is preferably at the nozzle 15 to 30 kW / 1, in the entire reaction system 3 to 10 W / 1.

Der Produktaustrag aus dem System erfolgt kontinuierlich an beliebiger Stelle. Bevorzugt erfolgt der Produktaustrag im unteren Reaktorbereich am Boden des Reaktors oder insbesondere aus der äußeren Schlaufenströmung über eine Katalysatorabtrenneinheit oder ohne eine solche. Diese Abtrenneinheit kann ein Schwerkraftabscheider, z. B. ein Settler, ein Querstromfilter oder eine Zentrifuge sein. Der Katalysator kann vom Produkt abgetrennt und anschließend in das Reaktorsystem zurückgeführt werden. Bevorzugt erfolgt der Produktaustrag unter Rückhaltung des Katalysators. Das Amin kann danach nach den üblichen und bekannten Verfahren, beispielsweise durch Destillation oder Extraktion, gereinigt werden.Product discharge from the system takes place continuously at any point. The product discharge preferably takes place in the lower reactor region at the bottom of the reactor or in particular from the outer loop flow via a catalyst separation unit or without such. This separation unit can be a gravity separator, z. As a settler, a cross-flow filter or a centrifuge. The catalyst can be separated from the product and then returned to the reactor system. Preferably, the product is discharged while retaining the catalyst. The amine can then be purified by the usual and known methods, for example by distillation or extraction.

Im erfindungsgemäßen Verfahren wird die Mono- und/oder Polynitroverbindung in reiner Form, als Mischung mit dem entsprechenden Mono- und/oder Polyamin, als Mischung mit dem entsprechenden Mono- und/oder Polyamin und Wasser oder als Mischung mit dem entsprechenden Mono- und/oder Polyamin, Wasser und einem insbesondere alkoholischen Lösungsmittel eingesetzt. Die aromatische Mono- und/oder Polynitroverbindung wird fein verteilt in das Gemisch eingetragen. Vorzugsweise wird die Menge an Nitroverbindung, die nicht an der erfindungsgemäßen Stelle dosiert wird, in die Strahldüse eingetragen, besonders bevorzugt in den Mischraum der Düse.In the process of the invention, the mono- and / or Polynitroverbindung in pure form, as a mixture with the corresponding mono- and / or polyamine, as a mixture with the corresponding mono- and / or polyamine and water or as a mixture with the corresponding mono- and / or polyamine, water and a particular alcoholic solvent used. The aromatic mono- and / or Polynitroverbindung is finely divided into the mixture. Preferably, the amount of nitro compound which is not metered at the point according to the invention, introduced into the jet nozzle, more preferably in the mixing space of the nozzle.

Vorzugsweise werden im erfindungsgemäßen Verfahren aromatische Nitroverbindungen mit einer oder mehreren Nitrogruppen und 6 bis 18 C-Atomen, bsp. Nitrobenzole, wie z.B. o-, m-, p-Nitrobenzol, 1,3-Dinitrobenzol, Nitrotoluole, wie z.B. 2,4-, 2,6-Dinitrotoluol, 2,4,6-Trinitrotoluol, Nitroxylole, wie z.B. 1,2-Dimethyl-3-, 1,2 Dimethyl-4-, 1,4-Dimethyl-2-, 1,3-Dimethyl-2-, 2,4-Dimethyl-1- und 1,3-Dimethyl-5-nitrobenzol, Nitronaphthaline, wie z.B. 1-, 2-Nitronaphthalin, 1,5 und 1,8-Dinitronaphthalin, Chlornitrobenzole, wie z.B. 2-Chlor-1,3-, 1-Chlor-2,4-dinitrobenzol, o-, m-, p-Chlornitrobenzol, 1,2-Dichlor-4-, 1,4-Dichlor-2-, 2,4-Dichlor-1-und 1,2-Dichlor-3-nitrobenzol, Chlornitrotoluole, wie z.B. 4-Chlor-2, 4-Chlor-3-, 2-Chlor-4- und 2-Chlor-6-nitrotoluol, Nitroaniline, wie z.B. o-, m-, p- Nitroanilin; Nitroalkohole, wie z.B. Tris(hydroxymethyl)nitromethan, 2-Nitro-2-methyl-, 2-Nitro-2-ethyl-1,3-propandiol, 2-Nitro-1-butanol und 2-Nitro-2-methyl-1-propanol sowie beliebige Gemische aus zwei oder mehreren der genannten Nitroverbindungen eingesetzt.Preferably, in the process according to the invention aromatic nitro compounds having one or more nitro groups and 6 to 18 carbon atoms, bsp. Nitrobenzenes, such as o-, m-, p-nitrobenzene, 1,3-dinitrobenzene, nitrotoluenes, such as 2,4-, 2,6-dinitrotoluene, 2,4,6-trinitrotoluene, nitroxylols, such as 1,2 Dimethyl 3-, 1,2-dimethyl-4-, 1,4-dimethyl-2-, 1,3-dimethyl-2-, 2,4-dimethyl-1- and 1,3-dimethyl-5-nitrobenzene , Nitronaphthalenes such as 1-, 2-nitronaphthalene, 1,5 and 1,8-dinitronaphthalene, chloronitrobenzenes such as 2-chloro-1,3-, 1-chloro-2,4-dinitrobenzene, o-, m- , p-chloronitrobenzene, 1,2-dichloro-4-, 1,4-dichloro-2-, 2,4-dichloro-1- and 1,2-dichloro-3-nitrobenzene, chloronitrotoluenes, such as 4-chloro 2, 4-chloro-3, 2-chloro-4- and 2-chloro-6-nitrotoluene, nitroanilines such as o-, m-, p-nitroaniline; Nitro alcohols such as tris (hydroxymethyl) nitromethane, 2-nitro-2-methyl, 2-nitro-2-ethyl-1,3-propanediol, 2-nitro-1-butanol and 2-nitro-2-methyl-1-propanol and any mixtures of two or more of the nitro compounds mentioned.

Bevorzugt werden nach dem erfindungsgemäßen Verfahren aromatische Nitroverbindungen, vorzugsweise Mononitrobenzol, Methylnitrobenzol oder Methylnitrotoluol, und insbesondere 2,4-Dinitrotoluol oder dessen technische Gemische mit 2,6-Dinitrotoluol, wobei diese Gemische vorzugsweise bis zu 35 Gewichtsprozent, bezogen auf das Gesamtgemisch, an 2,6-Dinitrotoluol mit Anteilen von 1 bis 4 Prozent an vicinalem DNT und 0,5 bis 1,5 % an 2,5- und 3,5-Dinitrotoluol aufweisen, zu den entsprechenden Aminen hydriert.Are preferred by the novel aromatic nitro compounds, preferably mononitrobenzene, methylnitrobenzene or methylnitrotoluene, and in particular 2,4-dinitrotoluene or its technical mixtures with 2,6-dinitrotoluene, these mixtures preferably up to 35 weight percent, based on the total mixture of 2 , 6-dinitrotoluene having proportions of 1 to 4 percent of vicinal DNT and 0.5 to 1.5% of 2,5- and 3,5-dinitrotoluene, hydrogenated to the corresponding amines.

Insbesondere bei der Hydrierung von Dinitrotoluolisomeren zu den entsprechenden Toluylendiaminderivaten (TDA) kann das erfindungsgemäße Verfahren vorteilhaft eingesetzt werden. Die Bildung von hochmolekularen, teerartigen Nebenprodukten, die bei den Verfahren des Standes der Technik zu Ausbeuteverlusten sowie zum Verkleben und damit zur vorzeitigen Desaktivierung des Katalysators führte, konnte praktisch vollständig unterdrückt werden. Damit ist auch die Reinigung des TDA unkomplizierter als bei den Verfahren des Standes der Technik.In particular, in the hydrogenation of Dinitrotoluolisomeren to the corresponding Toluylendiaminderivaten (TDA), the inventive method can be used advantageously. The formation of high molecular weight, tarry by-products, which led in the methods of the prior art to yield losses and for bonding and thus premature deactivation of the catalyst could be almost completely suppressed. Thus, the cleaning of the TDA is less complicated than in the methods of the prior art.

Die Hydrierung des Dinitrotoluols kann in Lösung durchgeführt werden. Als Lösungsmittel werden die dafür üblichen Stoffe, insbesondere niedere Alkohole, vorzugsweise Ethanol, eingesetzt. Vorzugsweise wird die Hydrierung ohne Lösungsmittel durchgeführt. Das hat die Vorteile, daß das Volumen der Reaktionsmischung geringer ist, was eine kleinere Dimensionierung des Reaktors sowie der Pumpen und Rohrleitungen ermöglicht, daß Nebenreaktionen zwischen dem Lösungsmittel und den Edukten ausgeschlossen werden sowie der Aufwand für die Aufarbeitung der Endprodukte verringert wird.The hydrogenation of the dinitrotoluene can be carried out in solution. The solvents used are the customary substances, in particular lower alcohols, preferably ethanol. Preferably, the hydrogenation is carried out without a solvent. This has the advantages that the volume of the reaction mixture is lower, which allows smaller dimensions of the reactor and the pumps and pipelines, that side reactions between the solvent and the starting materials are excluded and the cost of working up the end products is reduced.

Zur Durchführung des erfindungsgemäßen Verfahrens werden die an sich bekannten Hydrierkatalysatoren für aromatische Nitroverbindungen verwendet. Es können homogene und/oder insbesondere heterogene Katalysatoren eingesetzt werden. Die heterogenen Katalysatoren werden in feinverteiltem Zustand eingesetzt und liegen in der Reaktionssuspension feinteilig suspendiert vor. Geeignete Katalysatoren sind Metalle der VIII. Nebengruppe des Periodensystems, die auf Trägermaterialien wie Aktivkohle oder Oxiden des Aluminiums, des Siliciums oder anderer Materialien aufgebracht sein können. Vorzugsweise werden Raney-Nickel und/oder geträgerte Katalysatoren auf Basis von Nickel, Palladium und/oder Platin verwendet.For carrying out the process according to the invention, the known hydrogenation catalysts for aromatic nitro compounds are used. It is possible to use homogeneous and / or in particular heterogeneous catalysts. The heterogeneous catalysts are used in finely divided state and are finely suspended in the reaction suspension before. Suitable catalysts are metals of VIII. Subgroup of the Periodic Table, which may be applied to support materials such as activated carbon or oxides of aluminum, silicon or other materials. Raney nickel and / or supported catalysts based on nickel, palladium and / or platinum are preferably used.

Durch die Dispergierung der einzelnen Reaktanden wird in Verbindung mit den übrigen Reaktionsparametern eine intensive Durchmischung aller Komponenten, bei hohen Stoffübergangskoeffizienten und hohen volumenspezifischen Phasengrenzflächen erreicht. Die Anordnung der Kühlrohre im Reaktor parallel zu den Reaktorwänden hat eine nahezu vollständige Gradientenfreiheit des Reaktorinhalts bezüglich der Reaktionstemperatur zur Folge. Durch Vermeidung örtlicher Überhitzungen werden Nebenreaktionen deutlich zurückgedrängt und Katalysatordesaktivierung weitgehend vermieden. Es werden damit selbst bei niedrigen Katalysatorkonzentrationen hohe Raum-Zeit-Ausbeuten bei hoher Selektivität erreicht.The dispersion of the individual reactants, in conjunction with the other reaction parameters, achieves intensive mixing of all components, with high mass transfer coefficients and high volume-specific phase boundary surfaces. The arrangement of the cooling tubes in the reactor parallel to the reactor walls has an almost complete gradient freedom of the reactor contents with respect to the reaction temperature result. By avoiding local overheating side reactions are clearly suppressed and catalyst deactivation largely avoided. It is thus achieved even at low catalyst concentrations high space-time yields at high selectivity.

Wie oben beschrieben, ist das erfindungsgemäße Verfahren besonders geeignet für die Hydrierung von Dinitrotoluol zu Toluylendiamin. Gerade bei dieser Reaktion kommt es bei den Verfahren des Standes der Technik zu ausgeprägten Nebenreaktionen mit der Bildung von teerartigen Bestandteilen. Die Herstellung von Toluylendiamin nach dem erfindungsgemäßen Verfahren erfolgt bei den für die Herstellung von aromatischen Aminen üblichen, oben aufgeführten Temperaturen und Drücken.As described above, the process according to the invention is particularly suitable for the hydrogenation of dinitrotoluene to toluenediamine. Precisely in the case of this reaction, pronounced side reactions with the formation of tarry constituents occur in the prior art processes. The preparation of toluenediamine by the novel process is carried out at the customary for the production of aromatic amines, the above temperatures and pressures.

Das erfindungsgemäße Verfahren hat mehrere Vorteile. Die Verteilung der Edukte in der Reaktionsmischung wird verbessert, was zu niedrigen Gehalten an Nebenprodukten und geringer Desaktivierung des Katalysators führt. Die Umsetzung der Nitroaromaten erfolgt vollständiger, das heisst die Konzentration von Nitroaromaten am Ausgang des Reaktors sinkt deutlich. Dies bietet die Möglichkeit die Raum-Zeit-Ausbeute im Reaktor zu erhöhen. Im Vergleich mit dem in WO 00/35852 beschriebenen Verfahren erfolgt noch einmal eine deutliche Reduzierung der Menge der Nitroaromaten im Endprodukt. Überraschenderweise wird die auch Alterung des Katalysators vermindert. Die Verweilzeit der Nitroaromaten im Reaktor wird erhöht, dadurch kann prinzipiell auch die Katalysatorkonzentration vermindert werden.The method according to the invention has several advantages. The distribution of the starting materials in the reaction mixture is improved, which leads to low levels of by-products and low deactivation of the catalyst. The implementation of the nitroaromatics is more complete, that is, the concentration of nitroaromatics at the outlet of the reactor drops significantly. This offers the possibility of increasing the space-time yield in the reactor. In comparison with the in WO 00/35852 described method takes place once again a significant reduction in the amount of nitroaromatics in the final product. Surprisingly, the aging of the catalyst is also reduced. The residence time of the nitroaromatics in the reactor is increased, thereby, in principle, the catalyst concentration can be reduced.

Durch die erfindungsgemäße Dosierung des Wasserstoffs kann der Energieeintrag in den Reaktor verringert werden, da der Wasserstoff den Gasgehalt und somit die Stofftransportleistung im Ringraum des Reaktors erhöht und durch seine Auftriebskraft die interne Schlaufenströmung stabilisiert. Der Leistungseintrag durch die Strahldüse und damit auch die Menge des äußeren Kreislaufs kann deutlich verringert werden. Neben der Energieeinsparung führt dies auch zu einer geringeren mechanischen Beanspruchung und somit zu einer längeren Lebensdauer des Katalysators.Due to the metering of the hydrogen according to the invention, the energy input into the reactor can be reduced because the hydrogen increases the gas content and thus the mass transport performance in the annulus of the reactor and stabilizes the internal loop flow by its buoyancy. The power input through the jet nozzle and thus also the amount of the outer circuit can be significantly reduced. In addition to the energy savings, this also leads to a lower mechanical stress and thus to a longer life of the catalyst.

Die Erfindung soll an dem nachfolgenden Beispiel näher beschrieben werden.The invention will be described in more detail in the following example.

Beispiel 1example 1

Es wird ein zylinderförmiger Reaktor mit einem außenliegenden Kreislauf mit Pumpe, einer Düse, einer Prallplatte im unteren Reaktorteil sowie einem konzentrischen Einsteckrohr eingesetzt. Das Reaktionsvolumen des Reaktors beträgt rund 12 m3. Der Reaktor ist mit 350 parallel geschalteten Fieldrohren (4) versehen, die insgesamt einer Kühlfläche von etwa 300 m2 entsprechen. Die Menge des in die Fieldrohre eingespeisten Kühlwassers betrug 250 m3/h, die Temperatur des in die Fieldrohre eingespeisten Kühlwassers lag bei 50°C.It is a cylindrical reactor with an external circuit with pump, a nozzle, a baffle plate in the lower part of the reactor and a concentric insert tube used. The reaction volume of the reactor is about 12 m 3 . The reactor is provided with 350 parallel field tubes (4), which correspond to a total cooling area of about 300 m 2 . The amount of cooling water fed into the field tubes was 250 m 3 / h, the temperature of the cooling water fed into the field tubes was 50 ° C.

Über einen Verteilerring mit 12 Austrittsöffnungen mit einem Durchmesser von je 5 mm wurden 7 t/h einer Dinitrotoluolschmelze, in die flüssige Reaktionsmischung oberhalb der Prallplatte eingeleitet. Durch gleichzeitiges Einleiten von 5200 Nm3/h Wasserstoff in den Gasraum des Reaktors wurde im Reaktor ein Druck von 25 bar aufrechterhalten. Durch einen unterhalb der Prallplatte angebrachten Verteilerring mit 30 Bohrungen mit einem Durchmesser von je 8 mm wurde Wasserstoff eingeleitet. Zur Aufrechterhaltung der Schlaufenströmung wurde im externen Produktkreislauf ein Volumenstrom von 500 m3/h umgewälzt. In der Reaktionsdüse herrschte ein Überdruck gegenüber dem Gasraum des Reaktors von rund 2,5 bar, der Leistungseintrag betrug 3,5 kW/m3. Die Reaktion verlief unter nahezu isothermen Bedingungen, da die entstehende Reaktionswärme bereits am Ort ihrer Entstehung abgeführt wurde. Die maximale Reaktionstemperatur im unteren Drittel des Reaktors betrug 125°C. Dem Reaktor wurden gleichzeitig unter Rückhaltung des Katalysators 4,64 t/h eines entsprechenden Diaminotoluolgemisches sowie 2,74 t/h Wasser über einen im äußeren Kreislauf installierten Querstromfilter kontinuierlich entnommen, was einer Raum-Zeit-Ausbeute von 400 kg Amingemisch/(m3·h) entsprach. Die Ausbeute an Diamin betrug, bezogen auf eingesetztes Dinitrotoluol, > 99 %. Bei der destillativen Aufarbeitung fielen 0,15 % niedrigsiedende Nebenprodukte ("Leichtsieder") und 0,75 % teerartige Produkte ("Hochsieder") an. Der Gehalt an Nitro- bzw. Aminonitroverbindungen im Produktaustrag lag unterhalb der Nachweisgrenze von 10 ppm. Eine merkliche Desaktivierung des eingesetzten Hydrierkontakts konnte für den oben beschriebenen Betriebszustand auch nach 100 h Reaktionszeit nicht festgestellt werden.7 t / h of a Dinitrotoluolschmelze were introduced into the liquid reaction mixture above the baffle plate via a distributor ring with 12 outlet openings with a diameter of 5 mm. By simultaneously introducing 5200 Nm 3 / h of hydrogen into the gas space of the reactor, a pressure of 25 bar was maintained in the reactor. Hydrogen was introduced through a distributor ring mounted below the baffle plate with 30 holes each with a diameter of 8 mm. To maintain the loop flow, a volume flow of 500 m 3 / h was circulated in the external product cycle. In the reaction nozzle there was an overpressure with respect to the gas space of the reactor of about 2.5 bar, the power input was 3.5 kW / m 3 . The reaction proceeded under almost isothermal conditions, since the resulting heat of reaction was already removed at the site of its formation. The maximum reaction temperature in the lower third of the reactor was 125 ° C. 4.64 t / h of a corresponding diaminotoluene mixture and 2.74 t / h of water were continuously withdrawn from the reactor via a cross-flow filter installed in the outer circuit, which gave a space-time yield of 400 kg of amine mixture / (m 3 · H) corresponded. The yield of diamine was, based on dinitrotoluene used,> 99%. In the work-up by distillation, 0.15% of low-boiling by-products ("low boilers") and 0.75% tarry products ("high boilers") were obtained. The content of nitro or Aminonitroverbindungen in the product discharge was below the detection limit of 10 ppm. An appreciable deactivation of the hydrogenation contact used could not be determined for the operating state described above, even after 100 hours of reaction time.

Claims (8)

  1. A process for preparing amines by hydrogenation of the corresponding nitroaromatics in a vertical reactor whose length is greater than its diameter and which has in its upper region a downward-directed jet nozzle via which the reaction mixture and, if desired, part of the starting materials are introduced, has an outlet at any point on the reactor via which the reaction mixture is conveyed in an external circuit by means of a transport device back to the jet nozzle and has a flow reversal in its lower region, wherein at least part of the hydrogen and/or nitroaromatic starting materials used is fed into the liquid phase of the reactor in such a way that they travel upward in the liquid phase.
  2. The process according to claim 1, wherein the nitroaromatics are introduced above the flow reversal.
  3. The process according to claim 1, wherein the reactor has an impingement plate arranged perpendicular to the reactor wall in its lower part.
  4. The process according to claim 1 or 2, wherein a concentric plug-in tube is installed in the reactor parallel to the reactor wall.
  5. The process according to any of claims 1 to 3, wherein the nitroaromatics are fed into the reactor between impingement plate and plug-in tube.
  6. The process according to any of claims 1 to 4, wherein the hydrogen is fed in between the bottom of the reactor and the plug-in tube.
  7. The process according to any of claims 1 to 5, wherein part of the hydrogen used is fed into the external circuit of the reactor.
  8. The process according to any of claims 1 to 6, wherein hydrogen is fed into the external circuit of the reactor in such an amount that the reaction mixture in the external circuit has a gas content in the range from 3 to 15% by weight.
EP03706422A 2002-02-15 2003-02-04 Method for the production of amines Expired - Lifetime EP1476418B1 (en)

Applications Claiming Priority (3)

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DE10206214 2002-02-15
DE10206214A DE10206214A1 (en) 2002-02-15 2002-02-15 Process for the production of amines
PCT/EP2003/001063 WO2003068724A1 (en) 2002-02-15 2003-02-04 Method for the production of amines

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EP1476418A1 EP1476418A1 (en) 2004-11-17
EP1476418B1 true EP1476418B1 (en) 2010-06-23

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US7542454B2 (en) * 2005-01-21 2009-06-02 Intel Corporation MIMO channel feedback protocols
US7750188B2 (en) * 2007-06-27 2010-07-06 H R D Corporation System and process for the production of aniline and toluenediamine
HUE026176T2 (en) 2010-01-14 2016-05-30 Bayer Ip Gmbh Method for producing aromatic amines in the liquid phase
EP2571844B1 (en) * 2010-05-17 2017-10-04 Basf Se Process for the preparation of tuluenediamine by hydrogenation of dinitrotoluene
KR20130136502A (en) 2010-12-06 2013-12-12 바스프 에스이 Method for producing aromatic amines
US8981155B2 (en) 2010-12-06 2015-03-17 Basf Se Process for preparing aromatic amines
JP2014515736A (en) * 2011-03-16 2014-07-03 ビーエーエスエフ ソシエタス・ヨーロピア Appropriate input of starting materials into the process of producing aromatic amines by hydrogenation of nitroaromatic compounds.
US8835688B2 (en) 2011-03-16 2014-09-16 Basf Se Optimized introduction of the starting materials for a process for preparing aromatic amines by hydrogenation of nitroaromatics
KR20140037139A (en) 2011-05-24 2014-03-26 바스프 에스이 Process for preparing polyisocyanates from biomass
US8933262B2 (en) 2011-05-24 2015-01-13 Basf Se Process for preparing polyisocyanates from biomass
DE102011082441A1 (en) 2011-09-09 2013-03-14 Evonik Oxeno Gmbh Jet loop reactor with nanofiltration
US8895783B2 (en) 2012-02-07 2014-11-25 Basf Se Monitoring of the stoichiometric ratio in the reaction of nitroaromatics with hydrogen
EP2812308B1 (en) * 2012-02-07 2016-04-20 Basf Se Monitoring the stochiometric ratio when converting nitroaromatics with hydrogen
EP3181220A1 (en) * 2015-12-16 2017-06-21 Basf Se A process for removing a heterogeneous catalyst from a reaction product and a process for producing an aromatic amine
CN109776332A (en) * 2019-02-22 2019-05-21 中海油天津化工研究设计院有限公司 A kind of method that continous way adds hydrogen to prepare 2,4- dimethylaniline
CN114307862A (en) * 2021-12-01 2022-04-12 中海油天津化工研究设计院有限公司 Method for preparing methyl substituted aniline through membrane dispersion hydrogenation

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DE19844901C1 (en) * 1998-09-30 1999-11-04 Bayer Ag Method for metering liquid polynitro-aromatic compounds into hydrogenation reactors
KR100655354B1 (en) 1998-12-12 2006-12-08 바스프 악티엔게젤샤프트 Method for producing amines

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DE50312829D1 (en) 2010-08-05
US20050119505A1 (en) 2005-06-02
JP4146801B2 (en) 2008-09-10
DE10206214A1 (en) 2003-08-28
JP2006508018A (en) 2006-03-09
EP1476418A1 (en) 2004-11-17
WO2003068724A1 (en) 2003-08-21
CN1633408A (en) 2005-06-29
PT1476418E (en) 2010-07-06
KR20040091017A (en) 2004-10-27
CN1275933C (en) 2006-09-20
US7064237B2 (en) 2006-06-20
ATE471926T1 (en) 2010-07-15
AU2003208788A1 (en) 2003-09-04

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